Unit II Statistical Thermodynamics

Introduction of statistical thermodynamics

Macroscopic and microscopic properties: Macroscopic (thermodynamic) properties can be

understood as an average over microscopic property, that is, observed value of dynamical
(microscopic) quantities.

Microstates and Macrostates:

 Macrostate = macroscopic state and microstate = microscopic state

 Microstates is the collection of all the possible states (with different positions and
momenta) accessible to the microscopic particle at the temperature through which the
given thermodynamic state (macrostate) can be realised.
 A macrostate is experimentally observable whereas the microstate is not.
 A macrostate is characterized by a distribution which gives the probability of finding
the microscopic particle in each accessible microstate at the given temperature.

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Thermodynamic Probability and most probable distribution
Relation between entropy and probability (Boltzmann-Planck equation)

The Boltzmann-Planck equation for entropy of a given system is,

𝑆 = 𝑘 ln 𝑤
where k is Boltzmann constant (1.38 x 10-23 J K-1), S is statistical entropy and w is the
weight of the most probable configuration of the system.

 As temperature increases, the statistical weight factor w increases (since more

configurations are possible) and hence entropy the entropy of the system increases.

 As temperature decreases, the statistical weight factor w decreases (since fewer

configurations are possible) and hence entropy of the system decreases.

 As temperature T→0, the statistical weight factor w becomes unity (since only one
configuration is possible for the system, that is, lowest energy level), therefore ln w = 0
and hence entropy of the system S→0. This is consistent with the Third law of
thermodynamics which states the entropy of all perfect crystals tend to zero as
temperature tends to zero.

2
Concept of thermodynamic and mathematical probabilities

1. The number of ways of distributing N distinguishable objects 𝑊(𝑁) would be:

𝑊(𝑁) = 𝑁. (𝑁 − 1). (𝑁 − 2). (𝑁 − 3) … … … . .3.2.1 = 𝑁!

2. The number of ways of arranging N distinguishable objects 𝑊(𝑁) in group of Nj is:

𝑁! 𝑁!
𝑊(𝑁) = =
𝑁 !𝑁 !…𝑁 ! ∏ 𝑁 !
This distribution is known as Boltzmann distribution, which involves the
distribution of N distinguishable particles with no restriction to the number of particles
occupying any energy state.

3. The number of ways of selecting N distinguishable objects from a set of M distinguishable

objects irrespective of the order of choice is given below:
𝑀!
𝑊(𝑁) =
𝑁! (𝑀 − 𝑁)!

4. The number of ways of arranging N indistinguishable objects into M distinguishable

containers such that there is not more than one object per container, provided that M>>N,
can be given as:
𝑀!
𝑊(𝑁) =
𝑁! (𝑀 − 𝑁)!
This distribution is known as Fermi-Dirac distribution, which involves the
distribution of N indistinguishable particles over g energy states (g >> N) such that no more
than one particle could occupy any given energy state as necessitated by the anti-symmetric
wavefunction (Pauli’s exclusion Principle) of Fermions (half integral spin).

5. The number of ways of arranging N indistinguishable objects into M containers with no

restriction on the number of objects per container,
(𝑀 + 𝑁 − 1)!
𝑊(𝑁) =
(𝑀 − 1)! 𝑁!
This distribution is known as Bose-Einstein distribution, which involves the
distribution of N indistinguishable particles over g energy states (g >> N) with no
restriction on occupancy of energy state as necessitated by the symmetric wavefunction of
Bosons (zero or integral spin).

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 Ensembles – Assembly of assemblies

Ensemble: Collection of independent systems that are macroscopically identical but

microscopically different.

Microcanonical ensemble (NVE ensemble):

 Number of particles (N), volume (V) and Energy (E) of the system are constant.
 Each system is separated by impermeable adiabatic walls
 Cannot exchange matter or energy with the surroundings
 Isolated (adiabatic) system – characterized by constant N, V and E

Canonical ensemble (NVT ensemble):

 Number of particles (N), volume (V) and temperature (T) of the system are constant.
 Each system is separated by impermeable diathermal walls (thermal equilibrium)
 Can exchange energy but not matter with the surroundings
 Closed (isothermal) system – characterized by constant N, V and T

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Grand canonical ensemble (μVT ensemble):
 Chemical potential (μ), volume (V) and temperature (T) of the system are constant.
 Each system is separated by permeable diathermal walls (thermal equilibrium)
 Can exchange both matter and energy with the surroundings
 Open (isothermal) system – characterized by constant μ, V and T

5
 Maxwell-Boltzmann Statistics

Consider a system of total energy E containing ‘N’ identical and distinguishable

particles (molecules) at a temperature T.

The Maxwell-Boltzmann distribution is derived by subjecting to the following constraints:

1. Total number of particles (N) remain constant, i.e., ∑ 𝑛 = 𝑁
2. Total energy of the system (E) does not change, i.e., ∑ 𝜀 𝑛 = 𝐸

The thermodynamic probability of the system or the number of ways of distributing N particles
among gi cells is given by,

𝑁!
𝑊=
𝑛!

ln 𝑊 = [ln 𝑁! − ln 𝑛 !]

The above expression can be simplified further by applying Stirling’s approximation as,

ln 𝑊 = [𝑁 ln 𝑁 − 𝑁 − 𝑛 ln 𝑛 + 𝑛 ]

Since lnW depends on all the ni, when there is an infinitesimally small change in configuration,
that is, when the value of ni changes to ni+dni, the function lnW changes to lnW+ dlnW, where
𝜕𝑙𝑛𝑊
𝑑𝑙𝑛𝑊 = 𝑑𝑛 = 0
𝜕𝑛

Since dni cannot be zero (dni ≠ 0), the term in the expression must be zero.

On differentiating with respect to ni, we get,

𝜕 ln 𝑊 1
= [0 − 𝑛 ∙ − ln 𝑛 + 1]
𝜕𝑛 𝑛
𝜕 ln 𝑊
= − ln 𝑛
𝜕𝑛
𝜕 ln 𝑊 1
= ln
𝜕𝑛 𝑛
The function is to be minimized subjecting them to the two constraints,

𝑑𝑛 = 𝑑𝑁 = 0; 𝜀 𝑑𝑛 = 𝑑𝐸 = 0

Using Lagrange method of undetermined multipliers,

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 𝜕𝑙𝑛𝑊
− 𝛼 − 𝛽𝜀 =0
𝜕𝑛

Substituting the expression for in the above expression, we get

1
ln − 𝛼 − 𝛽𝜀 = 0
𝑛
1
ln = 𝛼 + 𝛽𝜀
𝑛
1
=𝑒
𝑛
( )
𝑛 =𝑒
( )
If the degeneracy of the ’i’ state is gi, then 𝑛 = 𝑔 𝑒
The most probable distribution for Boltzons at a given temperature.

Maxwell-Boltzmann statistics to Partition function

From Maxwell-Boltzmann statistics,
( )
𝑛 =𝑒

𝑛 =𝑒 𝑒

𝑁=𝑒 𝑄

𝑒 = 𝑁/𝑄

Substituting the value of 𝑒 in the expression,

𝑁
𝑛 = 𝑒
𝑍
𝑛 𝑒
=
𝑁 𝑍
Here is the fraction of particles gives the fraction of particles occupying the ith energy

state or the probability of occupying the ith energy state. If the ith energy state is the lowest
energy state (ground state), then 𝑛 = 𝑛 and 𝜀 = 0,

𝑛 1 1
= (𝑜𝑟) 𝑄 = 𝑛
𝑁 𝑍
𝑁
Partition function (Z) can be defined as the reciprocal of the fraction of particles occupying the

lowest energy state.

7
Quantum Statistics – Fermi-Dirac and Bose-Einstein Statistics
Fermi-Dirac Statistics

Consider a system of total energy E containing ‘N’ identical and indistinguishable

particles (molecules) at a temperature T. Such particles with half-integral spin angular
momentum have anti-symmetric wavefunction are known as Fermions. e.g., electrons, protons.
The distribution of particles on discrete energy levels such as ε1, ε2, ε3, … εi is governed by
Pauli’s exclusion principle.
The Fermi-Dirac distribution is derived by subjecting to the following constraints:
3. Total number of particles (N) remain constant, i.e., ∑ 𝑛 = 𝑁
4. Total energy of the system (E) does not change, i.e., ∑ 𝜀 𝑛 = 𝐸
The thermodynamic probability of the system or the number of ways of distributing N particles
among gi cells is given by,

𝑔!
𝑊=
𝑛 ! (𝑔 − 𝑛 )!

ln 𝑊 = [ln 𝑔 ! − ln 𝑛 ! − ln(𝑔 − 𝑛 )!]

The above expression can be simplified further by applying Stirling’s approximation as,

ln 𝑊 = [𝑔 ln 𝑔 − 𝑔 − 𝑛 ln 𝑛 + 𝑛 − (𝑔 − 𝑛 ) ln(𝑔 − 𝑛 ) + (𝑔 − 𝑛 )]

ln 𝑊 = [ 𝑔 ln 𝑔 − 𝑛 ln 𝑛 − (𝑔 − 𝑛 ) ln(𝑔 − 𝑛 )]

Since lnW depends on all the ni, when there is an infinitesimally small change in configuration,
that is, when the value of ni changes to ni+dni, the function lnW changes to lnW+ dlnW, where
𝜕𝑙𝑛𝑊
𝑑𝑙𝑛𝑊 = 𝑑𝑛 = 0
𝜕𝑛

Since dni cannot be zero (dni ≠ 0), the term in the expression must be zero.

On differentiating with respect to ni, we get,

𝜕 ln 𝑊 1 1
= [0 − 𝑛 ∙ − ln 𝑛 − (𝑔 − 𝑛 ) ∙ ∙ (−1) − (−1) ln(𝑔 − 𝑛 )]
𝜕𝑛 𝑛 𝑔 −𝑛
𝜕 ln 𝑊 1
= [0 − 1 − ln 𝑛 + (𝑔 − 𝑛 ) ∙ + ln(𝑔 − 𝑛 )]
𝜕𝑛 𝑔 −𝑛
𝜕 ln 𝑊
= [−1 − ln 𝑛 + 1 + ln(𝑔 − 𝑛 )]
𝜕𝑛

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 𝜕 ln 𝑊
= [− ln 𝑛 + ln(𝑔 − 𝑛 )]
𝜕𝑛
𝜕 ln 𝑊 𝑔 −𝑛
= ln
𝜕𝑛 𝑛
The function is to be minimized subjecting them to the two constraints,

𝑑𝑛 = 𝑑𝑁 = 0; 𝜀 𝑑𝑛 = 𝑑𝐸 = 0

Using Lagrange method of undetermined multipliers,

𝜕𝑙𝑛𝑊
− 𝛼 − 𝛽𝜀 =0
𝜕𝑛

Substituting the expression for in the above expression, we get

𝑔 −𝑛
ln − 𝛼 − 𝛽𝜀 = 0
𝑛
𝑔 −𝑛
ln = 𝛼 + 𝛽𝜀
𝑛
𝑔 −𝑛
=𝑒
𝑛
𝑔
=1+𝑒
𝑛
𝑛 1
=
𝑔 𝑒 +1
The most probable distribution for Fermions at a given temperature.

9
 Bose -Einstein Statistics

Consider a system of total energy E containing ‘N’ identical and indistinguishable

particles (molecules) at a temperature T. Such particles with integral spin angular momentum
have symmetric wavefunction are known as Bosons. e.g., photons, plasmons.The distribution
of particles on discrete energy levels such as ε1, ε2, ε3, … εi with no restriction on occupation.

The Bose-Einstein distribution is derived by subjecting to the following constraints:

1. Total number of particles (N) remain constant, i.e., ∑ 𝑛 = 𝑁
2. Total energy of the system (E) does not change, i.e., ∑ 𝜀 𝑛 = 𝐸

The thermodynamic probability of the system or the number of ways of arranging n i particles
among gi cells is given by,

(𝑛 + 𝑔 − 1)!
𝑊=
𝑛 ! (𝑔 − 1)!

ln 𝑊 = [ln(𝑛 + 𝑔 − 1)! − ln 𝑛 ! − ln(𝑔 − 1)!]

The above expression can be simplified further by applying Stirling’s approximation as,

ln 𝑊 = [(𝑛 + 𝑔 − 1) ln(𝑛 + 𝑔 − 1) − (𝑛 + 𝑔 − 1) − 𝑛 ln 𝑛 + 𝑛

− (𝑔 − 1) ln(𝑔 − 1) + (𝑔 − 1)]

ln 𝑊 = [ (𝑛 + 𝑔 − 1) ln(𝑛 + 𝑔 − 1) − 𝑛 ln 𝑛 − (𝑔 − 1) ln(𝑔 − 1)]

Since lnW depends on all the ni, when there is an infinitesimally small change in configuration,
that is, when the value of ni changes to ni+dni, the function lnW changes to lnW+ dlnW, where
𝜕𝑙𝑛𝑊
𝑑𝑙𝑛𝑊 = 𝑑𝑛 = 0
𝜕𝑛

Since dni cannot be zero (dni ≠ 0), the term in the expression must be zero.

On differentiating with respect to ni, we get,

𝜕 ln 𝑊 1 1
= [(𝑛 + 𝑔 − 1) ∙ + ln(𝑛 + 𝑔 − 1) − 𝑛 ∙ − ln 𝑛 + 0]
𝜕𝑛 (𝑛 + 𝑔 − 1) 𝑛
𝜕 ln 𝑊
= [1 + ln(𝑛 + 𝑔 − 1) − 1 − ln 𝑛 ]
𝜕𝑛

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 𝜕 ln 𝑊
= ln(𝑛 + 𝑔 − 1) − ln 𝑛
𝜕𝑛
The term (ni + gi -1) can be written as (ni + gi), since the term ‘1’ is negligible compared to
the value of (ni + gi),
𝜕 ln 𝑊
= [ln(𝑛 + 𝑔 ) − ln 𝑛 ]
𝜕𝑛
𝜕 ln 𝑊 𝑔 +𝑛
= ln
𝜕𝑛 𝑛
The function is to be minimized subjecting them to the two constraints,

𝑑𝑛 = 𝑑𝑁 = 0; 𝜀 𝑑𝑛 = 𝑑𝐸 = 0

Using Lagrange method of undetermined multipliers,

𝜕𝑙𝑛𝑊
− 𝛼 − 𝛽𝜀 =0
𝜕𝑛

Substituting the expression for in the above expression, we get

𝑔 +𝑛
ln − 𝛼 − 𝛽𝜀 = 0
𝑛
𝑔 +𝑛
ln = 𝛼 + 𝛽𝜀
𝑛
𝑔 +𝑛
=𝑒
𝑛
𝑔
=𝑒 −1
𝑛
𝑛 1
=
𝑔 𝑒 −1
The most probable distribution for Bosons at a given temperature.

Comparison (attached separately)

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 Partition Function

Partition function is a characteristic of a system and is denoted by Z. Partition function

is defined as the sum of the probability factor for different energy levels. Therefore, partition
function can be defined as the sum of terms over all accessible quantum states which could be
written as,

𝑧= g𝑒

In Boltzmann distribution law, the partition function appears as the normalizing factor
to find the fraction of particles occupying the ith energy state,
𝑛 𝑔𝑒 𝑔𝑒
= =
𝑁 ∑ g𝑒 𝑍
Here the exponential 𝑔 𝑒 indicates the occupation number (ni) of the ith energy
state. If the ith energy state is the ground state, then Ei = 0, the expression becomes, =

Thus, partition function (Z) can be defined as the reciprocal of the fraction of particles
occupying the lowest energy state.

Characteristics of Partition function:

1. It indicates the mode of distribution of particles in various energy states.
2. It is a pure number, hence dimensionless quantity.
3. The lowest value of partition function would be g0 at absolute zero temperature where
all the particles occupy the lowest energy state. (The lowest value is ONE if g0 = 1 and
could never be zero or less than one)
4. The partition function increases with increase in temperature as the particles start
occupying higher energy stats and so partition function tends to infinity as temperature
of the system tends to infinity, i.e., T ∞, Z  ∞,
5. Partition function is an indicative of the average number of energy states that are
thermally accessible at the given temperature.

Partition function plays a role in statistical thermodynamic very similar to the role of
wavefunction in Quantum mechanics as both of them seem to contain all dynamical
information about the system. Above all, partition function functions not merely as a
normalization factor and an important quantity from which other thermodynamic functions

12
such as pressure (P), internal energy (E), enthalpy (H), entropy (S), Helmholtz free energy (A),
Gibbs free energy (G), chemical potential (μ), heat capacity (CV) so on and so forth can be
calculated.

Molecular Partition Function

The partition function of a given atom/molecule is given by the expression,

/
𝑞= 𝑔𝑒

where g is the degeneracy of the energy levels and E is the corresponding energy. It is
clear from the above expression that partition function a quantity that is the summation over
all accessible energy levels for the given atom/molecule at a particular temperature.
The molecular partition function of a given molecule is given by,
𝑞 = 𝑞 .𝑞 .𝑞 .𝑞 .𝑞
where qt, qr, qv, qe and qn are the translational, rotational, vibrational, electronic and
nuclear partition functions.

Translational Partition Function:

Consider an atom/molecule of mass m moving along the x-axis in a 1-D box of length L, the
translational energy levels of the atom/molecule become quantized. The allowed energy levels
(En) are given by the expression,
𝑛 ℎ
𝐸 =
8𝑚𝐿
Where n is the quantum number and can take only positive integers.
The energy difference of various higher energy levels with respect to the lower energy level is
given by,
𝑛 ℎ ℎ ℎ
𝜀 = − = (𝑛 − 1) = (𝑛 − 1) 𝜀
8𝑚𝐿 8𝑚𝐿 8𝑚𝐿
The translational partition function is given by the expression,

𝑞 = 𝑒

Since the translation energy levels are closely spaced (more closed with increase in mass of
the atom/molecule) and hence summation can be replaced by integral,

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 𝑞 = 𝑒 𝑑𝑛 ≈ 𝑒 𝑑𝑛

Substitute x2 = n2βε, then 2x dx = 2n dn β ε; substituting the values of in the above expression

we get, (dn = dx (1/βε)1/2)

1
𝑞 = 𝑒 𝑑𝑥
𝛽𝜀

1 √𝜋
𝑞 =
𝛽𝜀 2
Substituting the values of β = 1/kT and ε = h2/8mL2 in the above expression, we get,

2𝜋𝑚𝑘𝑇 𝐿
𝑞 = .𝐿 =
ℎ 𝜆
where λ is the thermal de Broglie wavelength of the atom/molecule with dimension of length.
It can also be written for an atom/molecule in a 3-D cube of length L and volume V as,
/ /
2𝜋𝑚𝑘𝑇 2𝜋𝑚𝑘𝑇
𝑞 = ∙ 𝐿 = ∙ 𝑉
ℎ ℎ
For an atom/molecule in a 3-D box of length, breadth and height a, b and c respectively,
/
2𝜋𝑚𝑘𝑇
𝑞 = ∙ 𝑎𝑏𝑐
ℎ
Rotational Partition Function:
Consider a rigid rotor molecule of moment of inertia I rotating along a given axis whose
rotational energy levels of the atom/molecule are quantized. The possible rotational energy
levels (EJ) are given by the expression,
ℎ
𝐸 = 𝐽 (𝐽 + 1)
8𝜋 𝐼
where J is rotational quantum number and can take from zero and all positive integers.
The energy difference of various higher energy levels with respect to the lower energy level is
given by,
ℎ ℎ
𝜀 = 𝐽 (𝐽 + 1) − 0 = 𝐽 (𝐽 + 1) = ℎ𝑐𝐵 𝐽 (𝐽 + 1)
8𝜋 𝐼 8𝜋 𝐼
The rotational partition function is given by the expression,

(2𝐽 + 1)𝑒 ( )
𝑞 =

(2𝐽 + 1)𝑒 ( )
𝑞 = 𝑑𝐽

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 ( )
𝑞 = 𝑒

1 𝑘𝑇 8𝜋 𝐼𝑘𝑇
𝑞 = = =
𝛽ℎ𝑐𝐵 ℎ𝑐𝐵 ℎ

The rotational partition function is divided by a factor known as symmetry number σ to account
for the symmetry of the molecule, that is, distinct number of ways by which the molecule can
be brought into identical configuration by rotations.
𝑘𝑇 𝑇
𝑞 = =
𝜎ℎ𝑐𝐵 𝜎 𝜃
where the rotational temperature θr = hcB/k is characteristic of the molecule.

It is therefore clear that the value of σ for hetereonuclear diatomic and asymmetric linear
polyatomic molecules is equal to 1 whereas the value of σ for homonuclear diatomic and
symmetric linear polyatomic molecules is 2. The σ value for non-linear molecules are to be
calculated and some are given here: Water Ammonia σ = 2, methane σ = 12, ethylene σ =4 and
benzene σ =12.
For polyatomic molecules it can be written as,

√𝜋 𝑇
𝑞 =
6 𝜃 𝜃 𝜃

Vibrational Partition Function:

Consider a diatomic molecule approximated as a 1-D harmonic oscillator of internuclear
distance re vibrating along a given axis where the vibrational energy levels are quantized. The
possible vibrational energy levels (Ev) are given by the expression,
1
𝐸 = 𝑣+ ℏω
2

where v is vibrational quantum number and can take from zero and all positive integers.
The energy difference of various higher energy levels with respect to the lower energy level is
given by,
1 1
𝜀 = 𝑣+ ℏω − ℏω = 𝑣 ℏω
2 2
Considering the fact that the vibrational energy levels are degenerate, the vibrational partition
function can be given by the expression,

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 ℏω/
𝑞 = 𝑒

ℏω/ ℏω/ ℏω/ ℏω/

𝑞 =1+𝑒 + 𝑒 + 𝑒 +𝑒 +⋯
1
𝑞 =
1 − 𝑒 ℏω/

Substituting the characteristic vibrational temperature 𝜃 = ℏω/𝑘 is characteristic of the

molecule.
1
𝑞 = /
1−𝑒
For molecules with lower vibrational frequency (weaker bonds) and at high temperature, the
above expression can be approximated as,
1 𝑘𝑇
𝑞 = =
1 − (1 − 𝜃 /𝑇) ℏω

Electronic Partition Function:

The electronic partition function of an atom/molecule is given by the expression,
/
𝑞 = 𝑔𝑒

where g is the degeneracy of various electronic energy levels and E is the

corresponding energy.

Nuclear Partition Function:

The nuclear partition function of an atom/molecule is given by the expression,
/
𝑞 = 𝑔𝑒

where g is the degeneracy of various nuclear energy levels and E is the corresponding
energy.

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Thermodynamic functions in terms of partition functions - calculation of
equilibrium constants

Calculation of equilibrium constant:

For the chemical reaction,
aA+bB⇌cC+dD
The equilibrium constant is written as,
[𝐶][𝐷]
𝐾=
[𝐴][𝐵]
Substituting the partition function of a molecule 𝑞 = 𝑞 𝑒 ∆ /
in the above expression,
(𝑞 ) (𝑞 ) ∆ /
𝐾= 𝑒
(𝑞 ) (𝑞 )
where ∆rE0 is the difference in energy between the ground states of the products and
reactants in the reaction and q is the molecular partition function component of each component
per unit volume.

Statistical approach to Thermodynamic properties:

Pressure as a function of Partition Function:

Pressure can be defined in terms of Helmholtz energy as,
𝜕𝐴
𝑃=−
𝜕𝑉
Substituting the value of S in the above expression, we obtain,
𝜕 ln 𝑄
𝑝 = 𝑘𝑇
𝜕𝑉

Internal Energy as a function of Partition Function:

The average energy is obtaining by multiplying the energy levels of each i th state Ei with the
corresponding probability and summing over all accessible quantum states at the temperature,
𝐸 1
𝐸= = 𝑛𝐸
𝑁 𝑁
/
Substituting the value of 𝑛 = 𝑔 𝑒 in the expression,

1
= 𝐸𝑔𝑒
𝑄
Partition function is given by the expression,

17
 𝑄= 𝑔𝑒

Differentiating the above expression with respect to temperature, we get,

𝜕𝑄 𝐸𝑔
= 𝑒
𝜕𝑇 𝑘𝑇
𝜕𝑄 1
= 𝐸𝑔 𝑒
𝜕𝑇 𝑘𝑇
Substituting the above expression in the expression for 𝐸 ,
1 𝜕𝑄
𝐸 = 𝑘𝑇 ∙ ∙
𝑄 𝜕𝑇
𝜕𝑙𝑛𝑄
𝐸 = 𝑘𝑇 ∙
𝜕𝑇

Entropy as a function of Partition Function:

𝐶
𝑆 −𝑆 = 𝑑𝑇
𝑇

specific heat capacity at constant volume, 𝐶 = =

1 𝜕 𝑘𝑇 𝜕𝑙𝑛𝑄
𝑆 −𝑆 = 𝑑𝑇
𝑇 𝜕𝑇 𝜕𝑇
𝐸
𝑆 −𝑆 = + 𝑘𝑙𝑛 𝑄
𝑇
𝜕𝑙𝑛 𝑄
𝑆 − 𝑆 = 𝑘𝑇 + 𝑘𝑙𝑛 𝑄
𝜕𝑇
Enthalpy as a function of Partition Function:
Enthalpy is given by the expression,
H = E +PV
Substituting the value of E and V in the above expression, we obtain,
𝜕𝑙𝑛𝑄 𝜕 ln 𝑄
𝐻 = 𝑘𝑇 + 𝑘𝑇𝑉
𝜕𝑇 𝜕𝑉
Gibbs free energy as a function of Partition Function:
Gibbs free energy is given by the expression,
G = H-TS
Substituting the value of H and S in the above expression, we obtain,
𝜕 ln 𝑄
𝐺 = 𝑘𝑇𝑉 − 𝑘𝑇 𝑙𝑛 𝑄
𝜕𝑉

18
Helmholtz free energy (A) as a function of Partition Function:
Helmholtz free energy is given by the expression,
A = E-TS
Substituting the value of S in the above expression, we obtain,
𝐸
𝐴= 𝐸−𝑇 + 𝑘𝑙𝑛 𝑄
𝑇
𝐴 = − 𝑘𝑇 𝑙𝑛 𝑄
Residual entropy:
For solids, the entropy is non-zero even at absolute zero due to the presence of disorder
in the crystal, which is referred to as residual entropy. The residual entropy of a given system is
calculated using the equation,
𝑆 = 𝑘 ln 𝑤
where k is Boltzmann constant (1.38 x 10-23 J K-1), S is statistical entropy and w is the
weight of the most probable configuration of the system.
Let us consider molecules like NO, where two molecular orientations are equally
probable. The number of probable arrangements for N molecules (w) would be 2 N. Then, the
entropy would be,
𝑆 = 𝑘 ln(2) = 𝑅𝑙𝑛 2

The residual molar entropy of Rln 2 is calculated to be 5.76 J K-1 mol-1 for molecules that adopt
two orientations at absolute zero.
Eg. Three orientations – R ln 3, four orientations – R ln 4

Equilibrium constant: (refer page no. 17)

Chemical potential as a function of Partition Function:

Chemical potential of a component i in a mixture is given in terms of A by the expression,
𝜕𝐴
𝜇 =
𝜕𝑛 , ,

𝜕 ln 𝑄
𝜇 = −𝑘𝑇
𝜕𝑛 , ,

Heat capacity as a function of Partition Function:

𝜕𝐸 𝜕 𝑘𝑇 𝜕𝑙𝑛𝑄
𝐶 = =
𝜕𝑇 𝜕𝑇 𝜕𝑇

19
 Heat Capacity of Monoatomic Gases

The amount of energy required to raise the temperature of one kilogram of the substance
by one kelvin is known as specific heat capacity. The SI unit for specific heat capacity is the
J·kg-1·K-1. The amount of energy required to raise the temperature of one mole of the substance
by one kelvin is known as molar heat capacity and is expressed in J·mol -1·K-1.
By heat capacity, it is often referred that heat capacity at constant volume, which is more
fundamental than the heat capacity at constant pressure. The heat capacity at constant volume
is defined as,
𝜕𝐸
𝐶 =
𝜕𝑇
where E is the energy, and T is temperature. The following are the two important experimental
facts about the heat capacity of solids:

1. In room temperature range, the value of the heat capacity of nearly all monoatomic solids is
close to 3Nk which is numerically equal to 24.94 JK -1 or 5.96 cal K-1.
2. At lower temperatures the heat capacity drops rapidly and approaches zero as T 3 in insulators
and as T in metals. If metal becomes semiconductor, the drop is observed to be faster than T.

20
Heat Capacity of Diatomic Gases - Ortho and Para hydrogen
In homonuclear diatomic molecules like hydrogen molecule, the nuclear spin of both
the hydrogen atom may align or oppose each other. If both the spins align with each other
(parallel spin), it is will result in triplet state and is referred to as ortho hydrogen. If the spins
oppose each other (anti-parallel spin), it will result in singlet state and is referred to as singlet
state. In case of fermion nuclei like hydrogen atom, the total wavefunction (ψ = ψ r ψn) is
antisymmetric with respect to the interchange of nuclei. Consequently, the product of rotational
wavefunction and nuclear wavefunction must be antisymmetric and therefore ψ r and ψn should
have opposite symmetry. If ψr is symmetrical (even J value), the accessible nuclear spin states
are odd. If ψr is anti-symmetrical (odds J values), the accessible nuclear spin states are even.
The total partition function, which is the product of rotational and vibrational partition
function, can be written as,
𝐽(𝐽 + 1)𝜃
𝑧 = 𝐼(2𝐼 + 1) (2𝐽 + 1) exp − +
𝑇
, , ,

𝐽(𝐽 + 1)𝜃
(𝐼 + 1) (2𝐼 + 1) (2𝐽 + 1) exp −
𝑇
. . ,

The spin of hydrogen nucleus I = ½

𝐽(𝐽 + 1)𝜃
𝑧 =1 (2𝐽 + 1) exp − +
𝑇
, , ,

𝐽(𝐽 + 1)𝜃
3 (2𝐽 + 1) exp −
𝑇
. . ,

The above expression with partition function (zrn) can be used to calculate the heat
capacity at constant volume (Cvrn). When the composition of ortho-to-par equilibrium mixture
is fixed as 3:1 by experimental conditions, the theoretically calculated curve of heat capacity
((from partition function) as a function of temperature agrees well with the experimental curve.

21
 HEAT CAPACITY OF SOLIDS-EINSTEIN AND DEBYE MODELS

EINSTEIN MODEL FOR HEAT CAPACITY OF SOLIDS

Einstein treated the atoms in a crystal as N independent (non-interacting)

three-dimensional simple harmonic oscillators, where all vibrating at the same frequency.
Einstein recognized that Planck’s quantization of the molecular oscillators in the walls of the
blackbody cavity was a universal property of the molecular oscillators in all solids.
Accordingly, the average energy of the oscillators was not the 3kT of kinetic theory, but rather
that derived in Planck’s development of the emission spectrum of a blackbody. Therefore, the
average number of phonons as a function of energy (distribution function) is given by,
1
<𝑛 >=
𝑒ℏ / −1
The average energy of an oscillator <E> of frequency ω as a function of energy could be
calculated by the product of Energy (hω) and <n> as follows,
ℏ𝜔
<𝐸 >=
𝑒ℏ / −1
Accounting for the N oscillators vibrating at the same frequencyin all three dimensions (3
degrees of freedom), the average energy is multiplied by 3N as shown below,
3𝑁ℏ𝜔
𝐸 =
𝑒ℏ / −1
𝜕𝐸 ℏ𝜔 𝑒ℏ /
𝐶 = = 3𝑁𝑘
𝜕𝑇 𝑘 𝑇 (𝑒 ℏ / − 1)
Substituting in the above expression ℏω/kB =θE, which is known as Einstein temperature, the
characteristic of a solid reflecting the rigidity of the lattice.
/
θ 𝑒
𝐶 = 3𝑁𝑘 /
𝑇 (𝑒 − 1)

(i) At very low temperature, that is, when T 0, then 𝑒 ℏ /

≫1
ℏ𝜔 𝑒ℏ /
3𝑁 ℏω ℏ /
𝐶 = 3𝑁𝑘 = 𝑒
𝑘 𝑇 (𝑒 ℏ / ) 𝑘 T
/
θ 𝑒 𝜃 /
𝐶 = 3𝑁𝑘 /
= 3Nk 𝑒
𝑇 (𝑒 ) 𝑇

(ii) The limiting value of Einstein heat capacity at high temperature, that is,

22
When T∞, then ℏω/kBT  0, so 𝑒 ℏ /
 0 and 𝑒 ℏ /
− 1 = ℏω/k T
ℏ𝜔 1
𝐶 = 3𝑁𝑘 = 3𝑁𝑘
𝑘 𝑇 ℏω
k T
θ 1
𝐶 = 3𝑁𝑘 = 3𝑁𝑘
𝑇 θ
T

Thus, the Einstein model for heat capacity reduces to Dulong-Petit’s law at high
temperature and it is observed to be independent of temperature.
It could be seen clearly that Einstein model successfully predicts that CV decreases with
decreasing T. However, the fall off is not as dramatic as predicted by the Einstein model.
According to the model, the specific heat capacity approaches zero exponentially as T0
which does not agree with the experimental results. At low temperature heat capacity is found
to have cubic dependence on temperature dependence (not exponential).

DEBYE MODEL FOR SPECIFIC HEAT CAPACITY OF SOLIDS

In his model, Debye treated the vibration of the lattice as phonons in a box, in contrast
to Einstein model, which treats the solid as non-interacting harmonic oscillators. As a result,
Debye model successfully predicted the low temperature T 3 dependence of heat capacity and
corroborated the experimental results. Moreover, it reduces to Dulong-Petit’s law at high
temperature limits like the Einstein model.

Debye Model: Energy of system = DOS x Phonon Energy x Average no. of Phonons (E,T)
i.e., 𝐸 = ∫ 𝑔(𝜔) ℏω n(ω) dω
9𝑁𝑘 𝑇 𝑥
𝐸= 𝑑𝑥
𝑇 𝑒 −1
where x = ℏω/kBT and xD = TD/T. Here the Debye temperature (TD = ℏωD/kB) is
associated with the highest allowed mode of vibration with the maximum frequency known as
Debye frequency (ωD).
The integral form of Energy cannot be evaluated in closed form, but numerical evaluation of
the integral shows reasonably good agreement with the observed specific heats of solids for the

23
full range of temperatures, approaching the Dulong-Petit law at high temperatures and the
characteristic T3 behavior at very low temperatures. The specific heat capacity as given by
Debye model is,
𝜕𝐸 9𝑁𝑘 𝑇 𝑥 𝑒
𝐶 = = 𝑑𝑥
𝜕𝑇 𝑇 (𝑒 − 1)
The agreement with the experimental results can also be understood from high and low
temperature limit as follows:
(i) High Temperature Limit:
/
9𝑁𝑘 𝑇 𝑥
𝐸= 𝑑𝑥
𝑇 𝑒 −1
At high temperature where T>>TD, x0 and ex1+x, the expression becomes
/
9𝑁𝑘 𝑇 𝑥 9𝑁𝑘 𝑇 𝑇
𝐸= 𝑑𝑥 = = 3𝑁𝑘 𝑇
𝑇 𝑥 𝑇 3𝑇
𝜕𝐸
𝐶 = = 3𝑁𝑘
𝜕𝑇
which is the Dulong-Petit law from classical thermodynamics.
(ii) Low Temperature Limit:
At low temperatures where T<< TD, the exponential in the denominator becomes very large
before reaching the limit, implying that the integrand is very small near the upper limit. This
makes it plausible to approximate the integral by increasing the limit to infinity (T/T D∞) to
make use of the standard integral.
9𝑁𝑘 𝑇 𝑥 9𝑁𝑘 𝑇 𝜋
𝐸= 𝑑𝑥 =
𝑇 𝑒 −1 𝑇 15
Therefore, the energy of the system is,
3𝜋 𝑁𝑘
𝐸= 𝑇
5𝑇
and the specific heat could be obtained as follows,
𝜕𝐸 12 𝑇
𝐶 = = 𝜋 𝑁𝑘
𝜕𝑇 5 𝑇
The Debye approximation is reasonable because according to the model only long
wavelength acoustic modes ћωD<kBT will only be excited to any appreciable extent at a given
low temperature T. In other words, Debye frequency, ω D = kTD/ћ, could be defined as the
highest frequency excited and the corresponding temperature is known as Debye temperature
(TD).

24
In conclusion, Debye theory of specific heat capacity shows T 3 approximation at low
temperature as obtained in the experimental results for non-metals.

25